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WO2022008229A1 - Réseau de systèmes et procédé pour l'exploitation d'un réseau de systèmes de ce type pour la production d'alcools supérieurs - Google Patents

Réseau de systèmes et procédé pour l'exploitation d'un réseau de systèmes de ce type pour la production d'alcools supérieurs Download PDF

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Publication number
WO2022008229A1
WO2022008229A1 PCT/EP2021/066958 EP2021066958W WO2022008229A1 WO 2022008229 A1 WO2022008229 A1 WO 2022008229A1 EP 2021066958 W EP2021066958 W EP 2021066958W WO 2022008229 A1 WO2022008229 A1 WO 2022008229A1
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Prior art keywords
gas
plant
alcohols
reformer
higher alcohols
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PCT/EP2021/066958
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German (de)
English (en)
Inventor
Nils Tenhumberg
Stefan Gehrmann
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ThyssenKrupp AG
ThyssenKrupp Industrial Solutions AG
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ThyssenKrupp AG
ThyssenKrupp Industrial Solutions AG
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Priority to US18/014,510 priority Critical patent/US20230219815A1/en
Priority to CN202180033522.XA priority patent/CN115552040A/zh
Priority to EP21739271.1A priority patent/EP4179121A1/fr
Publication of WO2022008229A1 publication Critical patent/WO2022008229A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B5/00—Making pig-iron in the blast furnace
    • C21B5/06—Making pig-iron in the blast furnace using top gas in the blast furnace process
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
    • C10K3/026—Increasing the carbon monoxide content, e.g. reverse water-gas shift [RWGS]
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/12—Making spongy iron or liquid steel, by direct processes in electric furnaces
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B7/00—Blast furnaces
    • C21B7/002—Evacuating and treating of exhaust gases
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
    • C21C5/28—Manufacture of steel in the converter
    • C21C5/285—Plants therefor
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/042—Purification by adsorption on solids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/042—Purification by adsorption on solids
    • C01B2203/043—Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14—Details of the flowsheet
    • C01B2203/148—Details of the flowsheet involving a recycle stream to the feed of the process for making hydrogen or synthesis gas
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B2100/00—Handling of exhaust gases produced during the manufacture of iron or steel
    • C21B2100/20—Increasing the gas reduction potential of recycled exhaust gases
    • C21B2100/22—Increasing the gas reduction potential of recycled exhaust gases by reforming
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B2100/00—Handling of exhaust gases produced during the manufacture of iron or steel
    • C21B2100/20—Increasing the gas reduction potential of recycled exhaust gases
    • C21B2100/24—Increasing the gas reduction potential of recycled exhaust gases by shift reactions
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B2100/00—Handling of exhaust gases produced during the manufacture of iron or steel
    • C21B2100/20—Increasing the gas reduction potential of recycled exhaust gases
    • C21B2100/28—Increasing the gas reduction potential of recycled exhaust gases by separation
    • C21B2100/282—Increasing the gas reduction potential of recycled exhaust gases by separation of carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B2100/00—Handling of exhaust gases produced during the manufacture of iron or steel
    • C21B2100/80—Interaction of exhaust gases produced during the manufacture of iron or steel with other processes
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C2100/00—Exhaust gas
    • C21C2100/02—Treatment of the exhaust gas
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/10—Reduction of greenhouse gas [GHG] emissions
    • Y02P10/143—Reduction of greenhouse gas [GHG] emissions of methane [CH4]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry

Definitions

  • the invention relates to a system network with a C0 2 -containing gases producing unit, a gas line system for C0 2 -containing gases and a gas / liquid separation plant.
  • the invention further relates to a method for producing higher alcohols from C0 2 -containing gases with a plant network comprising a C0 2 -containing gases producing unit, a gas line system for C0 2 -containing gases, a reformer, a reactor for the production of higher alcohols and a gas /Liquid Separation Plant.
  • Steel, pig iron and coke production produce large quantities of metallurgical gases, in particular blast furnace gas, converter gas and coke oven gas. Some of the gases can be recycled, but a not insignificant proportion is lost. However, this high degree of electricity generation is accompanied by high, undesirable CC emissions. This problem does not only exist in the field of steel, pig iron and coke production, but also applies to numerous other industrial applications with CO 2 -containing gas producing units.
  • SEHT Haldor Topse
  • Synthesis gases which mainly contain carbon monoxide and hydrogen, can be produced from natural gas and other gaseous and liquid hydrocarbons by means of steam reforming, partial oxidation, autothermal reforming and dry reforming getting produced.
  • the process for producing the synthesis gas can be selected depending on the desired synthesis gas composition, among other things.
  • Dry reforming describes the conversion of hydrocarbons such as methane with CO 2 to CO and hydrogen.
  • the hydrogen formed in the reaction tends to react with the C0 2 by means of reverse water gas shift reaction.
  • Typical catalysts for dry reforming are noble metal catalysts such as nickel or nickel alloys.
  • the autothermal reforming uses oxygen and CO 2 or water vapor to convert the methane into synthesis gas.
  • the methane is partially oxidized with oxygen.
  • Autothermal reforming is a combination of partial oxidation and steam reforming. Autothermal reforming combines the advantage of partial oxidation (provision of heat energy) with the advantage of steam reforming (higher hydrogen yield), which optimizes efficiency.
  • alkanes such as. eg methane and C0 2 formed as by-products.
  • Bastian Krause describes a process that is based on the production of higher alcohols from biomass generated synthesis gas is aligned.
  • the formed CO2 is removed in a complex C0 2 scrubbing, so that the CO2 is no longer available for the production of chemical compounds and the cleaned synthesis gas is then converted into alcohols.
  • the carbon efficiency is reduced by the C0 2 scrubbing, which is associated with a separation of the CO2.
  • the methane formed as a by-product is (partially) converted to synthesis gas via partial oxidation with oxygen.
  • the formation of the higher alcohols is described as a reaction sequence via the formation of CO by means of rWGS and subsequent conversion of the CO to higher alcohols.
  • the direct conversion of CO2 usually leads to the increased formation of by-products such as methane.
  • the previous conversion of CO2 to CO for example by means of a reverse water gas shift reaction, is therefore advantageous.
  • the invention is therefore based on the object of providing a plant network and a method for operating a plant network that make it possible in an economical and particularly efficient manner to process CO 2 -containing gas, in particular blast furnace gas and/or converter gas , to synthesize higher alcohols, in particular ethanol, propanol and butanol, thereby achieving the highest possible utilization of the carbon contained in CO and CO 2 while at the same time minimizing the required amount of H 2 , which has to be provided externally.
  • CO 2 -containing gas in particular blast furnace gas and/or converter gas
  • an aforementioned generic facility network wherein the facility network having an input connected to the gas line system reformer in which the C0 2 -containing gas with H 2 and / or hydrocarbons react 2 -containing synthesis gas mixture to a CO and H, the reformer is connected to a reactor for the production of higher alcohols, in which the synthesis gas mixture optionally reacts with further H 2 to form a gas-liquid mixture containing higher alcohols, and the gas/liquid separation plant for separating the alcohols from the gas-liquid mixture is connected to the reactor for production higher alcohols is connected.
  • the reformer can, for example, be a reformer for autothermal reforming or dry reforming.
  • V2 reaction of the synthesis gas mixture with H 2 to form a gas-liquid mixture containing higher alcohols in the reactor for the production of higher alcohols
  • V3 Separation of the alcohols of the gas-liquid mixture from the gas components in the gas/liquid separation plant.
  • the plant network according to the invention has a C0 2 -containing gases producing unit, for example a flot furnace for pig iron production and a converter steel mill for crude steel production, as well as a gas line system for the CO2-containing gases.
  • An essential component of the plant network according to the invention is that the plant network has a reformer connected to the gas line system.
  • the C0 2 -containing gas reacts with H2 and/or hydrocarbons to form a synthesis gas mixture containing CO and Fh, which serves as the starting material for the production of the higher alcohols.
  • the reaction of the synthesis gas mixture with H2 to form higher alcohols within the plant network according to the invention then takes place in one or more reactors for the production of higher alcohols.
  • the synthesis gas mixture is catalytically converted to a gas-liquid mixture containing higher alcohols. This significantly improves the C0 2 balance of the system network, especially if so-called green H2, which is produced, for example, by water electrolysis, is used.
  • the plant network according to the invention has a gas/liquid separation plant in which the alcohols, in particular the higher alcohols, and optionally also the alkanes and alkenes of the gas-liquid mixture are separated.
  • the alcohols obtained can then be marketed, for example, as a product mixture, in particular as a fuel additive, or separated into the individual alcohols in a distillation.
  • the alkanes and alkenes can also be put to industrial use, with the H2 contained in the alkanes preferably being recovered and the alkenes being used for further value creation.
  • the CO 2 -containing gas-producing unit comprises a blast furnace for pig iron production and a converter steelworks for crude steel production, the gas line system carrying the gas produced during pig iron production and/or crude steel production.
  • the plant network according to the invention can synthesize the C0 2 -containing blast furnace gas and/or converter gas to higher alcohols in an economically particularly efficient manner and thereby achieve the highest possible utilization of the carbon contained in CO and CO 2 .
  • the C0 2 -containing gas-producing unit also includes a coke oven system, with the gas line system including a gas distribution system for coke oven gas, which occurs during a coking process in the coke oven system.
  • the gas line system including a gas distribution system for coke oven gas, which occurs during a coking process in the coke oven system.
  • CO 2 -containing gases for the plant network according to the invention are, for example, flue gases, COREX or FINEX gases, industrial process gases from lime kilns, cement plants, biogas plants, bioethanol plants and waste incineration plants.
  • the plant network has a gas compression unit for compressing the gases to the respective reaction pressure in the reformer and the reactor for the production of higher alcohols.
  • the plant network according to the invention has a gas cleaning unit according to a preferred development.
  • the service life of the catalyst located in the reactor for the production of higher alcohols can be increased by aggressive components of the CO 2 -containing gases, in particular cyanides, sulfur or ammonium compounds, being removed.
  • the plant network according to the invention has a gas/liquid separation plant for separating the gas-phase and the liquid components of the product mixture of the alcohol reactor and for returning the gas components of the gas-liquid mixture to the reformer and/or to the reactor for the higher temperature vapor recovery line connected to alcohols.
  • the recirculation can take place either in the reformer, in order to convert possible by-products, in particular hydrocarbons present in the synthesis gas mixture, and CO 2 to CO, or in the reactor for the formation of higher alcohols, in order to increase the conversion of the synthesis gas.
  • the choice of reaction procedure i.e. the proportion of recirculation to the reformer and/or the reactor for the production of higher alcohols, depends on the concentration of hydrocarbons and CO 2 in the gas phase, since this allows the carbon efficiency to be optimized in a particularly advantageous manner .
  • the gas/liquid separation plant for returning the liquid components of the gas/liquid mixture, in particular higher hydrocarbons, which are contained as by-products in the liquid phase in the gas/liquid mixture, to the reformer is connected to the reformer Has feedback line. This can also further improve the carbon efficiency.
  • a discharge of the synthesis residual gas makes it possible, in a further development of the plant network according to the invention, to avoid a concentration of inert components.
  • the size of the plant is kept compact in an advantageous manner, since unnecessary entrainment of inert components in the gas is effectively avoided. This also reduces the system and operating costs.
  • a concentration of inert components, in particular N 2 can also be achieved by passing the gas components leaving the gas/liquid separation plant through a membrane to separate off nitrogen.
  • a pressure swing adsorption unit for the recovery of H 2 by pressure swing adsorption and subsequent recycling into the reformer and / or the output for discharging the synthesis residual gas Reactor connected for the production of higher alcohols.
  • This increase in the hydrogen yield can reduce the required amount of externally produced hydrogen, which further reduces the dependency on expensive external H2, which can also increase the cost-effectiveness of the plant network.
  • the reformer of the system combination according to the invention is designed for operation in the temperature range from 600 to 1200°C. This allows the equilibrium of the reverse water-gas shift reaction to be set in a particularly advantageous manner, in particular to be shifted to the product side. In the specified temperature range, a higher proportion of CO and H2O is reached as a state of equilibrium. It has been shown that in this way the recovery of higher alcohols in the reactor for the production of higher alcohols is carried out in a particularly efficient manner. A particularly high conversion of the CO2 in metallurgical gases to CO in the reformer is achieved in the temperature range from 1050 to 1150°C.
  • the inventive method is comprising a CO2-containing gas producing unit, a gas line system for C0 2 -containing gases, a reformer, a reactor for the production of higher alcohols and a gas / liquid separation unit performed in a system network.
  • the hydrocarbons are reacted with the CO 2 -containing gases and/or CO 2 and/or O 2 and/or H 2 O as oxygen sources to form a CO and H 2 -containing synthesis gas mixture in the reformer.
  • a second step of the process according to the invention comprises the reaction of the synthesis gas mixture, optionally with the addition of H2, to form a gas-liquid mixture containing higher alcohols in the reactor Production of higher alcohols.
  • a composition of the synthesis gas with an H2:CO ratio of 1:2 to 2:1 is preferably used here.
  • the alcohols in the gas-liquid mixture are separated from the gas components in the gas/liquid separation plant, so that the higher alcohols are produced in a carbon-efficient manner and can be separated into the different alcohols, for example, in a subsequent distillation.
  • the alkanes and alkenes are also particularly preferably separated off.
  • Gases containing CO 2 , coke oven gas and/or blast furnace gas and/or converter gas are particularly preferred, since the process according to the invention offers particular potential for improving carbon efficiency in the production of coke, crude steel or pig iron.
  • the CO 2 -containing gases are cleaned in a gas purification unit in the reformer and/or compressed in a gas compression unit before the reaction with H2 and/or hydrocarbons to give a CO and H2-containing synthesis gas mixture.
  • a minimum purity of the gas is ensured in order to protect the catalyst used in the production of the higher alcohols and on the other hand the gas is brought to a defined pressure which influences the reaction rate, in order to be able to optimally carry out the subsequent process steps, in particular the synthesis of higher alcohols.
  • the gas preferably compressed and cleaned
  • the gas is then passed into a reformer.
  • the gas reacts with H2 and/or hydrocarbons to form a synthesis gas mixture containing CO and H2, with CO2 and/or O2 and/or H2O being used as oxygen sources.
  • a synthesis gas mixture containing CO and H2
  • CO2 and/or O2 and/or H2O being used as oxygen sources.
  • methane the following reactions taking place in the reformer, which take place as a function of the concentrations of the respective components, are mentioned: Dry reforming: CH4 + C0 2 2 CO + 2 H 2
  • the synthesis gas generated by the reformer for the production of the higher alcohols is thus CO and C0 2 -containing (residual content of unreacted C0 2 ).
  • a special feature is that the high reaction temperatures of the reforming make it possible to adjust the equilibrium of the reverse water-gas shift reaction, optionally also with the addition of hydrogen and using a suitable catalyst for the reverse water-gas shift reaction, and in particular to to move the product page. It has been shown that this can significantly influence the efficiency of the conversion of the synthesis gas mixture into higher alcohols in the reactor downstream of the reformer for the production of higher alcohols. Temperatures of >600°C are required to shift the equilibrium of the water-gas shift reaction to the product side.
  • a particularly high conversion of C0 2 in metallurgical gases to CO in the reformer or water gas shift reaction reactor is achieved when the reformer or water gas shift reaction reactor is operated in the temperature range of 1050 to 1150°C.
  • the gas components are returned to the reformer and/or the reactor for the production of higher alcohols.
  • the carbon efficiency of the conversion of the synthesis gas into higher alcohols can be increased by converting the by-products produced into alcohols in a further process step.
  • the alkenes can be converted into alcohols, for example, by means of hydration.
  • C0 2 can be hydrogenated to CO via the reverse water gas shift reaction (rWGS).
  • the alkanes can be converted into synthesis gas, for example via steam reforming, partial oxidation, autothermal reforming and dry reforming, and returned to the process.
  • so-called green and possibly expensive hydrogen produced by means of renewable energies is used in the production of the higher alcohols is, conversion of the alkanes to synthesis gas is advantageous from an economic and ecological point of view with regard to the provision of hydrogen.
  • the reaction of the alkanes formed as a by-product and the CO 2 formed as a by-product and optionally the CO 2 or CO 2 -containing gases used as feed for the production of the synthesis gas can be carried out via dry reforming or autothermal Reforming, optionally with the addition of oxygen and / or water are advantageously combined in a reactor for synthesis gas production.
  • the CO 2 serves as a source of oxygen for reforming the alkanes.
  • the CO 2 is usually present in excess of the alkanes formed as by-products in the process for producing the higher alcohols.
  • the aim is therefore to convert the excess CO 2 into CO by means of a reverse water-gas shift reaction, if necessary with the addition of additional hydrogen.
  • the conversion of the CO 2 to CO and the shifting of the equilibrium of the water-gas shift reaction can preferably take place in the reactor for synthesis gas production (dry reforming or autothermal reforming) or in a downstream reactor.
  • the CO used as a feed for the production of the synthesis gas 2 or C0 2 -containing gas may be partially or completely directly to the reactor for the water-gas shift reaction is supplied.
  • the (thermal) energy required for the reforming (e.g. dry reforming) and the reverse water-gas shift reaction can be used in the inventive plant network of blast furnace, coking plant and plant for the production of the higher plant, for example by burning the blast furnace gas, the coke oven gas , the off-gas of the coke oven gas PSA or off-gases of the chemical plant.
  • the oxygen formed as a by-product can be used for the partial oxidation or autothermal reforming of the hydrocarbons.
  • the H 2 contained in the synthesis residual gas is recovered by pressure swing adsorption in a pressure swing adsorption unit and fed to the reformer and/or the reactor for the production of higher alcohols, thereby increasing the hydrogen yield and the dependency on external h sources, such as from an expensive water electrolysis, is reduced and the profitability is increased.
  • H2 is obtained from compressed coke oven gas by pressure swing adsorption in a pressure swing adsorption unit and fed to the reformer and/or the reactor for the production of higher alcohols.
  • the alkanes formed as by-products in the process for producing higher alcohols can advantageously be converted back into synthesis gas in the reformer due to the possible conversion of methane and other hydrocarbons in the reformer and fed back into the process.
  • methanol and/or the alkenes can also be converted back into synthesis gas in the reformer.
  • the alkenes can also be synthesized into higher alcohols to maximize higher alcohol production.
  • the reformer is particularly preferably operated in a temperature range from 600 to 1200.degree.
  • the method according to the invention makes use of the knowledge that this influences the efficiency of the synthesis of the higher alcohols by influencing the CO concentration in the reverse water-gas shift reaction through the selection of the temperature range.
  • the reaction conditions are chosen in such a way that a high CO 2 conversion is achieved and only little or no methane and/or alkanes are formed or remain in the gas mixture.
  • Fig. 2 A schematic representation of another invention
  • FIG. 3 A schematic representation of a further inventive
  • Fig. 4 A schematic representation of the method according to the invention.
  • FIG. 1 shows an example of a plant network 1 according to the invention, in which C0 2 -containing gases C from a C0 2 -containing gases producing unit are brought to a pressure that can be specified for the subsequent processes in a gas compression unit 2 in order to thereby increase the reaction rate for to set the subsequent chemical reactions.
  • the compressed C0 2 -containing gases are then cleaned in a gas cleaning unit 3 of chemical substances which impair the function and service life of the reactor's catalyst for the production of higher alcohols, in particular cyanides, sulfur and ammonium compounds.
  • hydrocarbons react with the C0 2 -containing gases C and/or CO2 and/or O2 and or H2O as oxygen sources to form a CO and Fh-containing synthesis gas mixture in a reformer 4.
  • the synthesis gas produced by the reformer 4 for the production of the higher Alcohols contain CO and C0 2 . It is particularly advantageous when using the reformer 4 that it can be used to adjust the equilibrium of the reverse water-gas shift reaction. Optimally, this is shifted to the product side so that a particularly high conversion of CO2, for example from metallurgical gases, to CO is achieved, which in turn increases the efficiency of the Synthesis of higher alcohols improved.
  • the gas-liquid mixture for separating the alcohols is fed into a gas/liquid separation plant 6 connected to the reactor 5, in which the higher alcohols, in particular ethanol, propanol and butanol, are separated and be separated into their individual components in a downstream distillation unit 7 .
  • the gas/liquid separation system 6 has a gas recycling line connected to the reformer 4 for returning the gas components of the gas-liquid mixture in order to recycle the gas components G to further improve the carbon efficiency.
  • the H2 for the reformer 4 and the reactor for the production of higher alcohols 5 is provided, among other things, via H2 recovery in a pressure swing adsorption unit 8 from the residual synthesis gas P leaving the reformer 4, which is separated from the gas components G in order to reduce dependence on external F sources or to increase H2 self-sufficiency.
  • H2 for the reformer 4 and the reactor for the further developed plant network according to the invention shown in FIG Production of higher alcohols 5 via the purification or recovery of H2 from coke oven gas (H2-rich) K by means of H2 recovery (pressure swing adsorption) and the recovery of H2 from the synthesis residual gas P.
  • FIG. 3 shows a further preferred embodiment of the system network according to the invention.
  • an additional reactor for optimizing/fine adjustment of the synthesis gas composition 4a is connected upstream of the reactor for the production of higher alcohols 5, in which in particular the equilibrium of the water-gas shift reaction can be adjusted, which further improves the efficiency in the production of higher alcohols can.
  • this plant network according to the invention has a further stage, which enables the alcohols to be separated from the hydrocarbons, for example a distillation unit 7. The separated hydrocarbons are fed to a hydration unit 9, in which the alkenes are converted into alcohols.
  • the alcohols obtained by the hydration are then separated from the alkanes and unreacted alkenes to be returned to the process in an alcohol/alkane separation device 10 .
  • the alkanes and alkenes are preferably recycled by being fed into the reformer.
  • process step VOa to protect the catalyst arranged in the reactor for the production of higher alcohols, aggressive components of the CO 2 -containing gases, in particular cyanides, sulfur or ammonium compounds, are removed in the gas cleaning unit in order to extend the service life of the catalyst located in the reactor for the production of higher alcohols increase.
  • the gases containing CO2 are then brought to a defined pressure VOb in a gas compression unit in order to be able to optimally carry out the following process steps.
  • a large number of different compressors can also be provided, since the gas purification and the gas synthesis take place at different pressures.

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Abstract

L'invention concerne un réseau de systèmes (1) comprenant une unité produisant des gaz C contenant du CO2, un système de guidage de gaz pour les gaz C contenant du CO2 et un système de séparation gaz/liquide (6), le réseau de systèmes (1) possédant un reformeur (4) raccordé au système de guidage de gaz, dans lequel le gaz C contenant du CO2 réagit avec H2 H et/ou des hydrocarbures pour former un mélange de gaz de synthèse contenant du CO et du H2, le reformeur (4) étant raccordé à un réacteur pour la production d'alcools supérieurs (5), dans lequel le mélange de gaz de synthèse réagit avec H2 H pour former un mélange gaz/liquide contenant des alcools supérieurs, et le système de séparation gaz/liquide (6) pour la séparation des alcools du mélange gaz/liquide étant raccordé au réacteur pour la production d'alcools supérieurs (5).
PCT/EP2021/066958 2020-07-07 2021-06-22 Réseau de systèmes et procédé pour l'exploitation d'un réseau de systèmes de ce type pour la production d'alcools supérieurs Ceased WO2022008229A1 (fr)

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US18/014,510 US20230219815A1 (en) 2020-07-07 2021-06-22 System network and method for operating a system network of this type for producing higher alcohols
CN202180033522.XA CN115552040A (zh) 2020-07-07 2021-06-22 用于制备高级醇的厂房群组和操作该类型厂房群组的方法
EP21739271.1A EP4179121A1 (fr) 2020-07-07 2021-06-22 Réseau de systèmes et procédé pour l'exploitation d'un réseau de systèmes de ce type pour la production d'alcools supérieurs

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DE102020208458.0A DE102020208458A1 (de) 2020-07-07 2020-07-07 Anlagenverbund sowie Verfahren zum Betrieb eines solchen Anlagenverbundes zur Herstellung höherer Alkohole

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WO2019037885A1 (fr) * 2017-08-23 2019-02-28 Thyssenkrupp Ag Ensemble d'installations pour la production de fonte brute procédé permettant le fonctionnement de l'ensemble d'installations
DE102018209042A1 (de) * 2018-06-07 2019-12-12 Thyssenkrupp Ag Anlagenverbund zur Stahlerzeugung sowie ein Verfahren zum Betreiben des Anlagenverbundes.

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WO2019037885A1 (fr) * 2017-08-23 2019-02-28 Thyssenkrupp Ag Ensemble d'installations pour la production de fonte brute procédé permettant le fonctionnement de l'ensemble d'installations
DE102018209042A1 (de) * 2018-06-07 2019-12-12 Thyssenkrupp Ag Anlagenverbund zur Stahlerzeugung sowie ein Verfahren zum Betreiben des Anlagenverbundes.

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